阅读说明：本技术 E-1-卤-3,3,3-三氟丙烯的制备方法 (Preparation method of E-1-halo-3, 3, 3-trifluoropropene ) 是由 贾晓卿 张妮 董利 张呈平 于 2021-03-30 设计创作，主要内容包括：本发明公开了E-1-卤-3,3,3-三氟丙烯的制备方法,在嵌段催化剂存在下,在管式反应器中,1,1,1,3,3-五氯丙烷与氟化氢发生气相氟化反应,得到主产物E-1-氯-3,3,3-三氟丙烯和少量产物Z-1-氯-3,3,3-三氟丙烯；进一步,在嵌段催化剂存在下,在管式反应器中,E-1-氯-3,3,3-三氟丙烯或/和Z-1-氯-3,3,3-三氟丙烯,与氟化氢发生气相氟化反应,得到主产物E-1,3,3,3-四氟丙烯。本发明方法的单程产率高；特别是对于第二步工艺,仅需要将第一步产物流中的HCl去除掉,余下物质添加新的HF后可以直接用于氟化反应。本发明中的嵌段催化剂均具有活性高、使用寿命长的特点。(The invention discloses a preparation method of E-1-halogen-3, 3, 3-trifluoropropene, which comprises the following steps of carrying out gas phase fluorination reaction on 1,1,1,3, 3-pentachloropropane and hydrogen fluoride in a tubular reactor in the presence of a block catalyst to obtain a main product E-1-chlorine-3, 3, 3-trifluoropropene and a small amount of a product Z-1-chlorine-3, 3, 3-trifluoropropene; further, in the presence of a block catalyst, in a tubular reactor, carrying out gas phase fluorination reaction on the E-1-chloro-3, 3, 3-trifluoropropene and/or the Z-1-chloro-3, 3, 3-trifluoropropene and hydrogen fluoride to obtain a main product E-1,3,3, 3-tetrafluoropropene. The method has high single-pass yield; in particular, for the second step process, only the HCl in the first product stream needs to be removed and the remaining material can be used directly for the fluorination reaction after addition of fresh HF. The block catalyst of the invention has the characteristics of high activity and long service life.)

A process for the preparation of E-1-halo-3, 3, 3-trifluoropropene, wherein halo = chloro or fluoro, characterized in that: the preparation method comprises the following steps:

a. in the presence of a block catalyst, carrying out gas phase fluorination reaction on 1,1,1,3, 3-pentachloropropane and hydrogen fluoride in a tubular reactor to obtain a main product E-1-chloro-3, 3, 3-trifluoropropene and a small amount of a product Z-1-chloro-3, 3, 3-trifluoropropene; and/or

b. In the presence of a block catalyst, carrying out gas-phase fluorination reaction on E-1-chloro-3, 3, 3-trifluoropropene and/or Z-1-chloro-3, 3, 3-trifluoropropene and hydrogen fluoride in a tubular reactor to obtain a main product E-1,3,3, 3-tetrafluoropropene and a small amount of products Z-1,3,3, 3-tetrafluoropropene and 1,1,1,3, 3-pentafluoropropane;

the block catalyst is composed of SbF₅、TiF₄、SnF₄、NbF₅、TaF₅、SbF₃Any one of the active components and molybdenum oxyfluoride Mo_xO_yF_zTungsten oxyfluoride W_aO_bF_c、FeF₃、CoF₂、NiF₂、ZnF₂、BaF₂、SrF₂、GaF₃、InF₃The valence state m of molybdenum in the molybdenum oxyfluoride is +2 to +6, the valence state n of tungsten in the tungsten oxyfluoride is +2 to +6, x, y, z, a, b and c are positive numbers, mx =2y + z, and na =2b + c.

2. The method of claim 1, wherein: the mass percentage of the active component and the carrier are respectively 1-30% and 70-99%.

3. The method of claim 2, wherein: the preparation method of the block catalyst comprises the following steps:

(1) dissolving soluble salt of carrier metal in water, then dropwise adding a precipitator to completely precipitate metal ions, adjusting the pH value to 7.0-9.0, fully precipitating the carrier metal ions under the condition of stirring, aging for 12-36 hours, filtering the formed slurry, drying for 6-24 hours at 100-250 ℃, crushing the solid, and performing compression moldingObtaining a carrier precursor; roasting the obtained carrier precursor for 6-24 hours at 300-500 ℃ in a nitrogen atmosphere, and activating the carrier precursor for 12-24 hours at 200-400 ℃ by using a mixed gas consisting of hydrogen fluoride and nitrogen in a molar ratio of 1: 2 to obtain the carrier, wherein the carrier is molybdenum oxyfluoride, tungsten oxyfluoride and FeF₃、CoF₂、NiF₂、ZnF₂、BaF₂、SrF₂、GaF₃、InF₃Any one of them;

(2) in a dry and high-purity nitrogen or helium or argon atmosphere, according to the mass percentage content of the block catalyst, mixing SbCl₅、TiCl₄、SnCl₄、NbCl₅、TaCl₅、SbCl₃Coating the precursor of any active component on molybdenum oxyfluoride, tungsten oxyfluoride and FeF ₃、CoF₂、NiF₂、ZnF₂、BaF₂、SrF₂、GaF₃、InF₃On any carrier to obtain a catalyst precursor;

(3) and (3) activating the catalyst precursor obtained in the step (2) for 6-24 hours at 200-400 ℃ by using a mixed gas consisting of hydrogen fluoride and nitrogen in a molar ratio of 1: 2 to prepare the block catalyst.

4. The production method according to claim 3, characterized in that: the soluble salt of the carrier metal is any one or more of molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexachloride, tungsten dichloride, tungsten trichloride, tungsten tetrachloride, tungsten pentachloride, tungsten hexachloride and chloride, nitrate or acetate of Fe, Co, Ni, Zn, Ba, Sr, Ga or In.

5. The production method according to claim 3, characterized in that: the precipitant is at least one or more of ammonia water, sodium hydroxide, potassium hydroxide, cesium hydroxide and rubidium hydroxide.

6. The method of claim 1, wherein: the reaction conditions of the gas phase fluorination reaction of the step a are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 100-300 ℃, and the mass ratio of 1,1,1,3, 3-pentachloropropane to hydrogen fluoride is 1: 5 to 30, and the contact time is 5 to 100 s.

7. The method of claim 6, wherein: the reaction conditions of the gas phase fluorination reaction of the step a are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 200-300 ℃, and the mass ratio of 1,1,1,3, 3-pentachloropropane to hydrogen fluoride is 1: 10 to 30, and the contact time is 30 to 100 s.

8. The method of claim 6, wherein: the reaction conditions of the gas phase fluorination reaction in the step b are as follows: the reaction pressure is 0.1 to 0.5MPa, the reaction temperature is 200 to 500 ℃, the amount ratio of E-1-chloro-3, 3, 3-trifluoropropene and/or Z-1-chloro-3, 3, 3-trifluoropropene to hydrogen fluoride is 1: 1 to 20, and the contact time is 0.1 to 100 s.

9. The method of claim 8, wherein: the reaction conditions of the gas phase fluorination reaction in the step b are as follows: the reaction pressure is 0.1 to 0.5MPa, the reaction temperature is 300 to 500 ℃, the amount ratio of E-1-chloro-3, 3, 3-trifluoropropene and/or Z-1-chloro-3, 3, 3-trifluoropropene to hydrogen fluoride is 1: 5 to 20, and the contact time is 6 to 100 s.

10. The production method according to any one of claims 1 to 9, characterized in that: the preparation method is a method for recycling and coproducing E-1-chloro-3, 3, 3-trifluoropropene and E-1,3,3, 3-tetrafluoropropene, and the product streams of the steps a and b are combined and treated to obtain the target E-1-chloro-3, 3, 3-trifluoropropene and E-1,3,3, 3-tetrafluoropropene, as well as a byproduct Z-1-chloro-3, 3, 3-trifluoropropene, Z-1,3, 3-tetrafluoropropene and 1,1,1,3, 3-pentafluoropropane, wherein part of the E-1-chloro-3, 3, 3-trifluoropropene and the byproduct Z-1-chloro-3, 3, 3-trifluoropropene are recycled to the reactor of the step b as the raw material of the step b, the by-products Z-1,3,3, 3-tetrafluoropropene and 1,1,1,3, 3-pentafluoropropane are recycled to the reactor of the gas phase fluorination reaction of step a or b to continue the reaction, and are converted into E-1,3,3, 3-tetrafluoropropene by the gas phase dehydrofluorination reaction of 1,1,1,3, 3-pentafluoropropane and the gas phase isomerization reaction of Z-1,3,3, 3-tetrafluoropropene under the action of the block catalyst.

Technical Field

The invention relates to a method for preparing E-1-halo-3, 3, 3-trifluoropropene (halo = fluoro or chloro) by catalytic fluorination with a block catalyst, in particular to a method for co-producing E-1-halo-3, 3, 3-trifluoropropene (halo = fluoro, chloro) by gas phase fluorination by taking 1,1,1,3, 3-pentachloropropane as a starting material, wherein the 1-halo-3, 3, 3-trifluoropropene comprises E-1,3,3, 3-tetrafluoropropene and E-1-chloro-3, 3, 3-trifluoropropene.

Background

At present, the following three types of methods are mainly used for synthesizing 1,1,1,3, 3-pentafluoropropane, E-1,3,3, 3-tetrafluoropropene or E-1-chloro-3, 3, 3-trifluoropropene from 1,1,1,3, 3-pentachloropropane as a starting material by gas phase fluorination reaction:

(1) ionic liquids

CN105849072A reports 300 g of hydrogen fluoride, 250 g of 1,1,1,3, 3-pentachloropropane, 6 g of EMIm (HF)_2.3F (EMIm means 1-ethyl 3-methylimidazole ) ionic liquid is put into a reactor at room temperature and mixed uniformly, wherein the mass ratio of the hydrogen fluoride to the 1,1,1,3, 3-pentachloropropane to the ionic liquid is 13:1:0.03, the reactor is heated to the required temperature, the temperature is slowly heated to about 110 ℃ for several hours and kept constant, and the pressure is controlled to be in the range of 1.90MPa-2.41 MPa by discharging HCl generated in the reaction to a dry ice cold trap. After 8 hours the reaction was complete (as determined by no HCl formation), the pressure from the reactor was vented to a dry ice cold trap. The crude product from the dry ice cold trap was transferred to an ilmiel absorber cartridge (frozen in dry ice) with about 400 grams of water. The absorption cylinder was allowed to slowly return to room temperature and a sample of the organic layer that had formed in the cylinder (aqueous layer and organic layer were present in the cylinder at the time of discharge) was taken out and passed through a gas chromatograph, with the result that: 3.0% of 1,1,1,3, 3-pentafluoropropane, 93.0% of E-1,3,3, 3-tetrafluoropropene and 3.0% of Z-1,3,3, 3-tetrafluoropropene.

（2）SbCl₅Or SbF₅Catalyst and process for preparing same

CN1063736C reports the addition of 8.7g SbCl to a 600mL Monel autoclave equipped with mechanical stirring₅And cooled to-27 ℃. The autoclave was then evacuated and filled with 49.8g of anhydrous HF. The contents were cooled to-40 ℃ and 44g of 1,1,1,3, 3-pentachloropropane were added. The reactor was then connected to a packed column/condenser assembly. The condenser was maintained at-20 ℃. The reaction mixture was heated over 2.25 hoursTo 135 ℃ and maintained at this temperature for 2 hours. During this heating, the pressure of the autoclave was reduced from a pressure above 2.66MPa to about 1.97MPa to 2.66MPa by periodic venting (HCl by-product). The discharge was discharged from the top of the condenser to a cold KOH water scrubber connected to a-78 ℃ cold trap. The reactor was then completely evacuated to a cold trap and 1,1,1,3, 3-pentafluoropropane collected in a 57% yield.

(3) Chromium-based catalyst

CN102211974A reported that 10ml of Zn modified chromium based catalyst was packed in an Inconel tubular reactor. Heating the reactor to 250 ℃ N₂After 2 hours of feeding at a rate of 10ml/min, N feeding was stopped₂. Introducing materials HF and 1,1,1,3, 3-pentachloropropane into a reactor at flow rates of 30ml/min and 10ml/min respectively, purifying a reaction crude product by a 10% KOH solution at 300 ℃ and collecting the reaction crude product in a cold trap to obtain a mixture of 1-chloro-3, 3, 3-trifluoropropene and 1,3,3, 3-tetrafluoropropene, wherein the content of the 1-chloro-3, 3, 3-trifluoropropene is 79.7%.

CN102844285A reports on fluorinated Cr₂O₃In the presence of the catalyst, 1,1,1,3, 3-pentachloropropane and HF are introduced, and the reaction conditions are as follows: the mass ratio of 1,1,1,3, 3-pentachloropropane and HF is 1: 9, the reaction temperature is 350 ℃, the contact time is 9.2s, the reaction pressure is 0.17MPa, and the reaction result is as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, and the selectivity of E-1-chloro-3, 3, 3-trifluoropropene was 80.42%.

CN106824232A reports fluorination of E-1-chloro-3, 3, 3-trifluoropropene with HF in the presence of a high-valent chromium-based catalyst, with the conditions: the reaction temperature is 400 ℃, and the material ratio of E-1-chloro-3, 3, 3-trifluoropropene to HF is 1: contact time 6s, reaction results are: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 79.1%, and the sum of the selectivities of E-1,3,3, 3-tetrafluoropropene and Z-1,3,3, 3-tetrafluoropropene was 75.3%.

The above prior art has the following disadvantages: (1) although the ionic liquid catalysis has the advantages of high selectivity and yield of the target product E-1,3,3, 3-tetrafluoropropene, the ionic liquid is too expensive and difficult to recycle; the process belongs to high-pressure intermittent reaction and has great potential safety hazard; (2) SbCl₅Or SbF₅The liquid phase fluorination of the catalyst belongs to an intermittent process in terms of process, the reaction pressure is high, the catalyst is difficult to recycle and easily generates a large amount of solid wastes and seriously pollutes the environment, the main product is 1,1,1,3, 3-pentafluoropropane, and the yield of the E-1-chloro-3, 3, 3-trifluoropropene is not disclosed, but the yield is less than 43 percent according to the literature, and the defect of low yield of the E-1-chloro-3, 3, 3-trifluoropropene exists; (3) the gas phase fluorination of the chromium-based catalyst has the defects of lower yield and lower selectivity of a target product E-1-chloro-3, 3, 3-trifluoropropene or E-1,3,3, 3-tetrafluoropropene.

Disclosure of Invention

The invention aims to overcome the defects in the background technology and provide the application of the block catalyst with high single-pass yield and high selectivity in the preparation of 1-halogen-3, 3, 3-trifluoropropene (halogen = fluorine or chlorine).

The invention also provides a block catalyst with high catalytic activity for catalyzing gas phase fluorination reaction.

To achieve the objects of the present invention, the present invention prepares E-1-halo-3, 3, 3-trifluoropropene (halo = fluoro or chloro) including E-1-chloro-3, 3, 3-trifluoropropene and E-1,3,3, 3-tetrafluoropropene by gas phase fluorination using 1,1,1,3, 3-pentachloropropane as a starting material, i.e.: (1) in the presence of a block catalyst, carrying out gas phase fluorination reaction on 1,1,1,3, 3-pentachloropropane and hydrogen fluoride in a tubular reactor to obtain a main product E-1-chloro-3, 3, 3-trifluoropropene and a small amount of Z-1-chloro-3, 3, 3-trifluoropropene; (2) in the presence of a block catalyst, carrying out gas-phase fluorination reaction on E-1-chloro-3, 3, 3-trifluoropropene and/or Z-1-chloro-3, 3, 3-trifluoropropene in a tubular reactor to obtain a main product E-1,3,3, 3-tetrafluoropropene, a small amount of Z-1,3,3, 3-tetrafluoropropene and 1,1,1,3, 3-pentafluoropropane. The reaction equation is as follows:

in the reaction (1), the main product E-1-chloro-3, 3, 3-trifluoropropene is obtained, and in the reaction (2), the main product E-1-chloro-3, 3, 3-trifluoropropene and the byproduct Z-1-chloro-3, 3, 3-trifluoropropene in the reaction (1) are used as raw materials, so that the main product E-1,3,3, 3-tetrafluoropropene is obtained. The raw material E-1-chloro-3, 3, 3-trifluoropropene and/or Z-1-chloro-3, 3, 3-trifluoropropene in the reaction (2) can be prepared by other methods, preferably by using the product of the first step of the present invention, i.e., only unreacted pentachloropropane and generated HCl in the product stream need to be separated, and the generated E-1-chloro-3, 3, 3-trifluoropropene and by-product Z-1-chloro-3, 3, 3-trifluoropropene and raw material HF directly enter the second step without separation to obtain E-1,3,3, 3-tetrafluoropropene.

A process for the preparation of E-1-halo-3, 3, 3-trifluoropropene, wherein halo = chloro or fluoro, comprising the steps of:

a. in the presence of a block catalyst, carrying out gas phase fluorination reaction on 1,1,1,3, 3-pentachloropropane and hydrogen fluoride in a tubular reactor to obtain a main product E-1-chloro-3, 3, 3-trifluoropropene and a small amount of a product Z-1-chloro-3, 3, 3-trifluoropropene; and/or

b. In the presence of a block catalyst, carrying out gas-phase fluorination reaction on E-1-chloro-3, 3, 3-trifluoropropene and/or Z-1-chloro-3, 3, 3-trifluoropropene and hydrogen fluoride in a tubular reactor to obtain a main product E-1,3,3, 3-tetrafluoropropene and a small amount of products Z-1,3,3, 3-tetrafluoropropene and 1,1,1,3, 3-pentafluoropropane;

the block catalyst is composed of SbF₅、TiF₄、SnF₄、NbF₅、TaF₅、SbF₃Any one of the active components and molybdenum oxyfluoride Mo_xO_yF_zTungsten oxyfluoride W_aO_bF_c、FeF₃、CoF₂、NiF₂、ZnF₂、BaF₂、SrF₂、GaF₃、InF₃The valence state m of molybdenum in the molybdenum oxyfluoride is +2 to +6, the valence state n of tungsten in the tungsten oxyfluoride is +2 to +6, x, y, z, a, b and c are positive numbers, mx =2y + z, and na =2b + c.

The mass percentage of the active component and the carrier are respectively 1-30% and 70-99%.

The preparation method of the block catalyst comprises the following steps:

(1) dissolving soluble salt of carrier metal in water, then dropwise adding a precipitator to enable metal ions to be completely precipitated, adjusting the pH value to 7.0-9.0, enabling the metal ions to be fully precipitated under the stirring condition, aging for 12-36 hours, filtering formed slurry, drying for 6-24 hours at 100-250 ℃, crushing obtained solid, and performing compression molding to obtain a carrier precursor; roasting the obtained carrier precursor for 6-24 hours at 300-500 ℃ in a nitrogen atmosphere, and activating the carrier precursor for 12-24 hours at 200-400 ℃ by using a mixed gas consisting of hydrogen fluoride and nitrogen in a molar ratio of 1: 2 to obtain the carrier, wherein the carrier is molybdenum oxyfluoride, tungsten oxyfluoride and FeF ₃、CoF₂、NiF₂、ZnF₂、BaF₂、SrF₂、GaF₃、InF₃Any one of them;

(2) in a dry and high-purity nitrogen or helium or argon atmosphere, according to the mass percentage content of the block catalyst, mixing SbCl₅、TiCl₄、SnCl₄、NbCl₅、TaCl₅、SbCl₃The precursor of any active component is uniformly coated on molybdenum oxyfluoride, tungsten oxyfluoride and FeF₃、CoF₂、NiF₂、ZnF₂、BaF₂、SrF₂、GaF₃、InF₃On any carrier to obtain a catalyst precursor;

(3) and (3) activating the catalyst precursor obtained in the step (2) for 6-24 hours at 200-400 ℃ by using a mixed gas consisting of hydrogen fluoride and nitrogen in a molar ratio of 1: 2 to prepare the block catalyst.

The soluble salt of the carrier metal is any one or more of molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexachloride, tungsten dichloride, tungsten trichloride, tungsten tetrachloride, tungsten pentachloride, tungsten hexachloride and chloride, nitrate or acetate of Fe, Co, Ni, Zn, Ba, Sr, Ga or In.

The precipitant is at least one or more of ammonia water, sodium hydroxide, potassium hydroxide, cesium hydroxide and rubidium hydroxide.

The reaction conditions of the gas phase fluorination reaction of the step a are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 100-300 ℃, and the mass ratio of 1,1,1,3, 3-pentachloropropane to hydrogen fluoride is 1: 5 to 30, and the contact time is 5 to 100 s.

The reaction conditions of the gas phase fluorination reaction of the step a are as follows: the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 200-300 ℃, and the mass ratio of 1,1,1,3, 3-pentachloropropane to hydrogen fluoride is 1: 10 to 30, and the contact time is 30 to 100 s.

The reaction conditions of the gas phase fluorination reaction in the step b are as follows: the reaction pressure is 0.1 to 0.5MPa, the reaction temperature is 200 to 500 ℃, the amount ratio of E-1-chloro-3, 3, 3-trifluoropropene and/or Z-1-chloro-3, 3, 3-trifluoropropene to hydrogen fluoride is 1: 1 to 20, and the contact time is 0.1 to 100 s.

The reaction conditions of the gas phase fluorination reaction in the step b are as follows: the reaction pressure is 0.1 to 0.5MPa, the reaction temperature is 300 to 500 ℃, the amount ratio of E-1-chloro-3, 3, 3-trifluoropropene and/or Z-1-chloro-3, 3, 3-trifluoropropene to hydrogen fluoride is 1: 5 to 20, and the contact time is 6 to 100 s.

The method is a method for recycling and coproducing E-1-chloro-3, 3, 3-trifluoropropene and E-1,3,3, 3-tetrafluoropropene, and the product streams of the steps a and b are combined and treated to obtain the target E-1-chloro-3, 3, 3-trifluoropropene and E-1,3,3, 3-tetrafluoropropene, and a byproduct Z-1-chloro-3, 3, 3-trifluoropropene, Z-1,3, 3-tetrafluoropropene and 1,1,1,3, 3-pentafluoropropane, wherein part of the E-1-chloro-3, 3, 3-trifluoropropene and the byproduct Z-1-chloro-3, 3, 3-trifluoropropene are recycled to the reactor of the step b as the raw material of the step b, the by-product Z-1,3,3, 3-tetrafluoropropene and 1,1,1,3, 3-pentafluoropropane are recycled to the reactor for the vapor phase fluorination reaction of step (a) or (b) and are converted into E-1,3,3, 3-tetrafluoropropene by vapor phase dehydrofluorination reaction of 1,1,1,3, 3-pentafluoropropane and vapor phase isomerization reaction of Z-1,3,3, 3-tetrafluoropropene under the action of a block catalyst.

The method for preparing the E-1-halogen-3, 3, 3-trifluoropropene can be used for independently preparing or coproducing two types of hydrofluoroolefins, namely the E-1,3,3, 3-tetrafluoropropene and the E-1-chlorine-3, 3, 3-trifluoropropene, and the production process belongs to a gas phase independent circulation continuous process method. The separation devices such as a distillation tower, a hydrogen fluoride adsorption tower, a hydrogen fluoride desorption tower and the like are adopted to realize the effective separation of all components in the product flow, and high-purity E-1,3,3, 3-tetrafluoropropene and high-purity E-1-chloro-3, 3, 3-trifluoropropene are obtained respectively. Wherein:

(1) separation in a first distillation column: the product stream composed of E-1,3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane, 1,1,1,3, 3-pentachloropropane, HCl and HF enters a first distillation tower for separation, the overhead component is HCl, the bottom component is E-1,3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane, 1,1,1,3, 3-pentachloropropane and HF;

(2) and (3) separating in a second distillation column: the product stream composed of E-1,3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane, 1,1,1,3, 3-pentachloropropane and HF enters a second distillation tower for separation, the tower top component is E-1,3,3, 3-tetrafluoropropene (boiling point is-19 ℃/760), the tower bottom component is Z-1, 3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane, 1,1,1,3, 3-pentachloropropane and HF, wherein the tower top components can be extracted out of the system, and a target product E-1,3,3, 3-tetrafluoropropene can be obtained through acid removal, dehydration and rectification;

(3) And (3) separating by using a third distillation column: a product stream consisting of 1,1,1,3, 3-pentachloropropane, Z-1, 3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane and HF enters a third distillation tower for separation, wherein the tower bottom component is 1,1,1,3, 3-pentachloropropane, and the tower top component is Z-1, 3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane and HF;

(4) separation in a hydrogen fluoride adsorption tower: feeding a product stream composed of Z-1, 3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane and HF into a hydrogen fluoride adsorption column filled with sulfuric acid having a concentration of 98% for adsorption separation, wherein the lower liquid phase is an inorganic phase rich in HF and sulfuric acid, and the upper liquid phase is an organic phase rich in Z-1, 3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane;

(5) hydrogen fluoride desorption column separation: an inorganic phase consisting of HF and sulfuric acid enters a hydrogen fluoride desorption tower for separation, the tower kettle component is sulfuric acid, and the tower top component is HF;

(6) And (3) separating by a fourth distillation column: and a mixture consisting of Z-1, 3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene and 1, 1, 1, 3, 3-pentafluoropropane enters a fourth distillation tower for separation, the tower bottom components comprise Z-1-chloro-3, 3, 3-trifluoropropene and E-1-chloro-3, 3, 3-trifluoropropene, the tower top components comprise Z-1, 3,3, 3-tetrafluoropropene and 1, 1, 1, 3, 3-pentafluoropropane, and the tower top components are recycled to the second reactor for continuous reaction and are converted into E-1, 3,3, 3-tetrafluoropropene.

(7) And (3) separating by a fifth distillation column: separating the mixture consisting of E-1-chloro-3, 3, 3-trifluoropropene and Z-1-chloro-3, 3, 3-trifluoropropene in a fifth distillation tower, wherein the overhead component is the E-1-chloro-3, 3, 3-trifluoropropene (the boiling point is 21 ℃/760 mmHg), the bottom component is the Z-1-chloro-3, 3, 3-trifluoropropene (the boiling point is 39 ℃/760 mmHg), the overhead component can be used for extracting a system, a target product, namely the E-1-chloro-3, 3, 3-trifluoropropene, can be obtained by acid removal, dehydration and rectification, the bottom component can also be recycled to the second reactor for continuous reaction, is converted to the E-1, 3,3, 3-tetrafluoropropene, and the bottom component can be recycled to the second reactor for continuous reaction, to E-1, 3,3, 3-tetrafluoropropene,

The type of reactor used for the reaction of the present invention is not critical, and a tubular reactor, a fluidized bed reactor, etc. may be used. Alternatively, adiabatic reactors or isothermal reactors may be used.

The invention has the advantages that:

(1) the method adopts 1,1,1,3, 3-pentachloropropane to synthesize E-1-chloro-3, 3, 3-tetrafluoropropene or E-1,3,3, 3-tetrafluoropropene, and has high single-pass yield; especially for the process of step b, only HCl in the product stream of step a needs to be removed, and the rest can be directly used for the fluorination reaction after adding new HF; meanwhile, the invention can also simultaneously co-produce E-1-chloro-3, 3, 3-tetrafluoropropene and E-1,3,3, 3-tetrafluoropropene, the product streams after the reactions in the steps a and b are jointly processed, and separated target products, namely E-1-chloro-3, 3, 3-tetrafluoropropene and E-1,3,3, 3-tetrafluoropropene can be extracted from the system, wherein part of E-1-chloro-3, 3, 3-tetrafluoropropene can also be used as the raw material in the step b; and the by-product can be recycled to the reactor to prepare the E-1-chloro-3, 3, 3-tetrafluoropropene.

(2) The block catalyst has the characteristics of high activity and long service life;

(3) the invention adopts a gas phase method to prepare E-1-chloro-3, 3, 3-tetrafluoropropene or E-1,3,3, 3-tetrafluoropropene, and carries out independent circulation on materials which are not completely reacted through a gas phase independent circulation process, so that the initial raw materials can be almost completely converted into the target product, and finally the target product is extracted from a process system, thereby not generating liquid waste and waste gas and realizing green production.

Drawings

The invention is described in further detail below with reference to the accompanying drawings.

Fig. 1 is a process flow diagram for co-production of E-1-halo-3, 3, 3-trifluoropropene (halo = fluoro or chloro) starting from 1,1,1,3, 3-pentachloropropane.

The reference numerals in fig. 1 have the following meanings. Pipeline: 1. 2, 3, 5, 7, 8, 9, 10, 12, 13, 15, 16, 18, 19, 21, 22, 24, 25, 26, 27, 29, 30, 31, 33, 34, 35, 36, and 37; a first reactor: 4; a second reactor: 6; a first distillation column: 11; a second distillation column: 14; a third distillation column: 17; a fourth distillation column: 28; a fifth distillation column: 32, a first step of removing the first layer; hydrogen fluoride adsorption column: 20; hydrogen fluoride desorption column: 23.

Detailed Description

The invention is described in further detail below with reference to the accompanying drawings.

The present invention is described in further detail with reference to fig. 1. But not to limit the invention. Fresh 1,1,1,3, 3-pentachloropropane passes through line 1, together with fresh anhydrous hydrogen fluoride via line 2 and 1,1,1,3, 3-pentachloropropane recycled via line 19, and anhydrous hydrogen fluoride recycled via line 26, via line 3 into first reactor 4 packed with a block catalyst for the gas phase fluorination reaction, the reaction product stream consisting of E-1-chloro-3, 3, 3-trifluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, HCl, HF, and 1,1,1,3, 3-pentachloropropane. E-1-chloro-3, 3, 3-trifluoropropene and/or Z-1-chloro-3, 3, 3-trifluoropropene via line 36 and line 30, together with fresh anhydrous hydrogen fluoride via line 7 and anhydrous hydrogen fluoride recycled via line 25, are introduced via line 8 into the second reactor 6 packed with a block catalyst to undergo a gas phase fluorination reaction, and the reaction product stream is composed of E-1,3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane, HCl, HF and E-1-chloro-3, 3, 3-trifluoropropene. The product stream from the first reactor 4 passes through line 5 and the product stream from the second reactor 6 passes through line 10 along with line 9 and enters the first distillation column 11 for separation. The overhead component of the first distillation column 11 is HCl (boiling point: 85.05 ℃/760 mmHg), the bottom component is E-1,3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane, 1,1,1,3, 3-pentachloropropane and HF, the overhead component is taken out as a byproduct HCl or hydrochloric acid diluted to various concentrations through a line 12 and sold or used, and the bottom component is fed into the second distillation column 14 through a line 13 to be separated. The overhead component of the second distillation column 14 is E-1,3,3, 3-tetrafluoropropene (boiling point is-19 ℃/760 mmHg), the bottom component is Z-1, 3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane, 1,1,1,3, 3-pentachloropropane and HF, the overhead component can be extracted by 15 to obtain the target product E-1,3,3, 3-tetrafluoropropene through deacidification, dehydration and rectification, and the bottom component of the second distillation column 14 enters the third distillation column 17 through the pipeline 16 to be continuously separated. The third distillation tower 17 has a tower bottom component of 1,1,1,3, 3-pentachloropropane, a tower top component of Z-1, 3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane and HF, the tower bottom component circulates to the first reactor 4 through the pipeline 19 and the pipeline 3 to continue the reaction, and the tower bottom component enters the hydrogen fluoride adsorption tower 20 filled with sulfuric acid with the concentration of 98% through the pipeline 18 to be adsorbed and separated. The lower liquid phase of the hydrogen fluoride adsorption tower 20 is an inorganic phase rich in HF and sulfuric acid, the upper liquid phase is an organic phase rich in Z-1, 3,3, 3-tetrafluoropropene, Z-1-chloro-3, 3, 3-trifluoropropene, E-1-chloro-3, 3, 3-trifluoropropene, 1,1,1,3, 3-pentafluoropropane, the upper organic phase enters a fourth distillation tower 28 through a pipeline 21 for continuous separation, and the lower inorganic phase enters a hydrogen fluoride desorption tower 23 through a pipeline 22 for separation; the bottom component of the hydrogen fluoride desorption tower 23 is sulfuric acid, the top component is HF (boiling point is 19.5 ℃/760 mmHg), the bottom component circulates to the hydrogen fluoride adsorption tower 20 through a pipeline 27 for continuous use, the top component circulates to the second reactor 6 through a pipeline 24, a pipeline 25 and a pipeline 8 for continuous reaction, and can also circulate to the first reactor 4 through a pipeline 24, a pipeline 26 and a pipeline 3 for continuous reaction. The fourth distillation column 28 has Z-1-chloro-3, 3, 3-trifluoropropene (boiling point: 39 ℃/760 mmHg), E-1-chloro-3, 3, 3-trifluoropropene (boiling point: 21 ℃/760 mmHg), Z-1, 3, 3-tetrafluoropropene, 1,1,1,3, 3-pentafluoropropane as an overhead component, and the overhead component is circulated to the second reactor via the line 24, the line 25, and the line 9 to continue the reaction, wherein in the second reactor 6, Z-1, 3,3, 3-tetrafluoropropene may be subjected to isomerization reaction to give E-1,3,3, 3-tetrafluoropropene, and 1,1,3,3, 3-pentafluoropropane may be subjected to dehydrofluorination reaction to give E-1,3,3, 3-tetrafluoropropene and Z-1, 3,3, 3-tetrafluoropropene; the tower bottom components of the fourth distillation tower 28 enter a fifth distillation tower 32 through a pipeline 31 for separation, the tower top components are E-1-chloro-3, 3, 3-trifluoropropene (the boiling point is 21 ℃/760 mmHg), the tower bottom components are Z-1-chloro-3, 3, 3-trifluoropropene (the boiling point is 39 ℃/760 mmHg), the tower top components can be taken out of the system through a pipeline 33 and a pipeline 34, the target product E-1-chloro-3, 3, 3-trifluoropropene can be obtained through acid removal, dehydration and rectification, the target product E-1-chloro-3, 3, 3-trifluoropropene can also be continuously circulated to the second reactor 6 through the pipeline 33, the pipeline 35, the pipeline 36, the pipeline 30 and the pipeline 8 for gas phase fluorination reaction to synthesize E-1,3, 3-tetrafluoropropene, the tower bottom components are continuously circulated to the second reactor 6 through the pipeline 37, the pipeline 36, the pipeline 30 and the pipeline 8 for gas phase fluorination reaction to synthesize E-1,3,3, 3-tetrafluoropropene.

An analytical instrument: shimadzu GC-2010, column model InterCap1 (i.d.0.25 mm; length 60 m; J & W Scientific Inc.).

Gas chromatographic analysis method: high purity helium and hydrogen were used as carrier gases. The temperature of the detector is 240 ℃, the temperature of the vaporization chamber is 150 ℃, the initial temperature of the column is 40 ℃, the temperature is kept for 10 minutes, the temperature is raised to 240 ℃ at the rate of 20 ℃/min, and the temperature is kept for 10 minutes.

Example 1

Preparation of a block catalyst: (1) dissolving tungsten trichloride in water, then dropwise adding ammonia water with the concentration of 10% by mass to completely precipitate metal ions, adjusting the pH value to 7.0-9.0, fully precipitating the tungsten trichloride under the stirring condition, aging for 24 hours, filtering the formed slurry, drying the slurry at 150 ℃ for 18 hours, crushing the solid, and performing compression molding to obtain a carrier precursor; roasting the obtained carrier precursor for 18 hours at 400 ℃ in a nitrogen atmosphere, activating the carrier precursor for 18 hours at 300 ℃ by using a mixed gas consisting of hydrogen fluoride and nitrogen with a molar ratio of 1: 2 to prepare a carrier, and determining that the carrier is tungsten oxyfluoride by XPS detection; (2) according to 20 percent of SbF in a block catalyst in a dry and high-purity nitrogen or helium or argon atmosphere₅Mixing with 80 percent of tungsten oxyfluoride by mass, and adding a precursor SbCl of an active component ₅Coating the tungsten oxyfluoride on the tungsten oxyfluoride to obtain a catalyst precursor; (3) activating the catalyst precursor obtained in the step (2) for 6-24 hours at 300 ℃ by using mixed gas consisting of hydrogen fluoride and nitrogen with the molar ratio of 1: 2 to prepare the block catalyst SbF₅Tungsten oxyfluoride.

A tubular reactor of 30cm length having an inner diameter of 1/2 inches was charged with 10 ml of a block catalyst. Heating the reactor to 250 ℃, introducing 1,1,1,3, 3-pentachloropropane and anhydrous hydrogen fluoride into the tubular reactor, and controlling the molar ratio of the 1,1,1,3, 3-pentachloropropane to the anhydrous hydrogen fluoride to be 1: 15, the contact time is 30 seconds, the reaction pressure is 0.1MPa, after 20 hours of reaction, the reaction product is washed by water and alkali, organic matters are obtained by separation, after drying and dewatering, the composition of the organic matters is analyzed by gas chromatography, and the reaction result is as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 95.4%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 4.5%.

Example 2

The same procedure as in example 1, except that the block catalyst was composed of 30% SbF₅And 70 percent of tungsten oxyfluoride, and the reaction temperature is changed to 100 ℃, and the reaction result is as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 54.6%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 99.1%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 0.9%.

Example 3

The same procedure as in example 1, except that the block catalyst was composed of 20% SbF₅And 80 percent of tungsten oxyfluoride, and the reaction temperature is changed to 150 ℃, and the reaction result is as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 71.6%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 97.4%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 2.6%.

Example 4

The same procedure as in example 1, except that the block catalyst was composed of 10% SbF₅And 90% tungsten oxyfluoride, and the reaction temperature is changed to 200 ℃, and the reaction result is as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 83.7%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 96.2%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 3.8%.

Example 5

The same procedure as in example 1, except that the block catalyst was prepared from 1% SbF₅And 99% tungsten oxyfluoride, and the reaction temperature is changed to 300 ℃, and the reaction result is as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 91.6%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 7.2%.

Example 6

The same operation as in example 1, except that the contact time was changed to 5 seconds, the reaction result was: the conversion of 1,1,1,3, 3-pentachloropropane was 72.8%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 97.2%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 2.8%.

Example 7

The same operation as in example 1, except that the contact time was changed to 100 seconds, the reaction result was: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 91.6%, the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 3.7%, and the selectivity for E-1,3,3, 3-tetrafluoropropene was 4.7%.

Example 8

The same operation as in example 1 was conducted, except that the molar ratio of 1,1,1,3, 3-pentachloropropane to anhydrous hydrogen fluoride was changed to 1: 5, the reaction result is: the conversion of 1,1,1,3, 3-pentachloropropane was 79.6%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 96.3%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 3.7%.

Example 9

The same operation as in example 1 was carried out, except that the molar ratio of 1,1,1,3, 3-pentachloropropane to anhydrous hydrogen fluoride was changed to: 1:10, and the reaction result is as follows: the conversion of 1,1,1,3, 3-pentachloropropane was 95.2%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 95.9%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 4.1%.

Example 10

The same operation as in example 1 was conducted, except that the molar ratio of 1,1,1,3, 3-pentachloropropane to anhydrous hydrogen fluoride was changed to 1: 30, the reaction result is: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 91.2%, the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 4.3%, and the selectivity for E-1,3,3, 3-tetrafluoropropene was 4.5%.

Example 11

The same operation as in example 1 was conducted, except that the reaction pressure was changed to 0.3MPa, and the reaction results were: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 94.2%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 5.8%.

Example 12

The same operation as in example 1 was conducted, except that the reaction pressure was changed to 0.5MPa, and the reaction results were: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 91.8%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 8.2%.

Example 13

The same operation as in example 1, except that molybdenum trichloride was replaced with tungsten trichloride to prepare a carrier, and XPS detection confirmed that the carrier was molybdenum oxyfluoride, "according to 20% SbF in a block catalyst₅Mixing with 80 percent of tungsten oxyfluoride by mass, and adding a precursor SbCl of an active component₅Coating on tungsten oxyfluoride "changed" to "according to 20% SbF in the blocked catalyst₅Mixing with 80 percent of molybdenum oxyfluoride by mass, and adding a precursor SbCl of an active component₅Coated on molybdenum oxyfluoride to prepare a block catalyst SbF₅Tungsten oxyfluoride 'change' to prepare block catalyst SbF₅Molybdenum oxyfluoride ", the reaction result is: the conversion of 1,1,1,3, 3-pentachloropropane was 100%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 93.5%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 6.4%.

Example 14

The same procedure as in example 1, except that tungsten trichloride was changed to ferric nitrate to prepare a carrier, which was confirmed to be FeF by XPS detection₃And will "according to 20% SbF in Block catalyst₅80 percent of tungsten oxyfluoride and a precursor SbCl of an active component₅Coating on tungsten oxyfluoride "changed" to "according to 20% TiF in the Block catalyst₄With 80% FeF₃Is prepared by mixing TiCl serving as a precursor of the active component₄Coated on FeF₃To "prepare a Block catalyst SbF₅Preparing TiF block catalyst from tungsten oxyfluoride₄/FeF₃", the reaction results are: the conversion of 1,1,1,3, 3-pentachloropropane was 98.2%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 96.1%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 3.8%.

Example 15

The same procedure as in example 1, except that barium nitrate was used instead of tungsten trichloride, was used to prepare a carrier, and XPS analysis confirmed that the carrier was BaF₂And will "according to 20% SbF in Block catalyst₅80 percent of tungsten oxyfluoride and a precursor SbCl of an active component₅Coating on tungsten oxyfluoride "changed" to "in accordance with block catalyst20% SbF₃With 80% BaF₂The mass percentage of the active component is that the precursor SbCl of the active component ₃Is coated on BaF₂To "prepare a Block catalyst SbF₅Tungsten oxyfluoride 'change' to prepare block catalyst SbF₃/BaF₂", the reaction results are: the conversion of 1,1,1,3, 3-pentachloropropane was 86.7%, the selectivity for E-1-chloro-3, 3, 3-trifluoropropene was 97.2%, and the selectivity for Z-1-chloro-3, 3, 3-trifluoropropene was 2.8%.

Example 16

Preparation of a block catalyst: a block catalyst, SbF, was prepared in the same manner as in example 1₅Tungsten oxyfluoride, SbF₅And tungsten oxyfluoride in a mass percentage of 20% and 80%.

A tubular reactor of 30cm length having an inner diameter of 1/2 inches was charged with 10 ml of a block catalyst. Heating the reactor to 400 ℃, introducing the E-1-chloro-3, 3, 3-trifluoropropene and anhydrous hydrogen fluoride into the tubular reactor, and controlling the molar ratio of the E-1-chloro-3, 3, 3-trifluoropropene to the anhydrous hydrogen fluoride to be 1: 10, the contact time is 6 seconds, the reaction pressure is 0.1MPa, after 20 hours of reaction, the reaction product is washed by water and alkali, organic matters are obtained by separation, after drying and dewatering, the composition of the organic matters is analyzed by gas chromatography, and the reaction result is as follows: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 100%, the selectivity for E-1,3,3, 3-tetrafluoropropene was 96.7%, and the selectivity for Z-1,3,3, 3-tetrafluoropropene was 3.2%.

Example 17

The same operation as in example 16 was carried out, except that the reaction temperature was changed to 200 ℃ to obtain the following reaction results: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 65.7%, the selectivity for E-1,3,3, 3-tetrafluoropropene was 46.8%, the selectivity for Z-1,3,3, 3-tetrafluoropropene was 6.3%, and the selectivity for 1,1,1,3, 3-pentafluoropropane was 46.9%.

Example 18

The same operation as in example 16 was carried out, except that the reaction temperature was changed to 300 ℃, and the reaction results were: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 87.2%, the selectivity for E-1,3,3, 3-tetrafluoropropene was 86.1%, the selectivity for Z-1,3,3, 3-tetrafluoropropene was 4.5%, and the selectivity for 1,1,1,3, 3-pentafluoropropane was 9.4%.

Example 19

The same operation as in example 16 was carried out, except that the reaction temperature was changed to 500 ℃ to obtain the following reaction results: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 100%, the selectivity for E-1,3,3, 3-tetrafluoropropene was 91.2%, the selectivity for Z-1,3,3, 3-tetrafluoropropene was 0.9%, and the selectivity for 3,3, 3-trifluoropropyne was 7.9%.

Example 20

The same operation as in example 16, except that the contact time was changed to 0.1 second, the reaction result was: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 48.6%, the selectivity for E-1,3,3, 3-tetrafluoropropene was 98.3%, and the selectivity for Z-1,3,3, 3-tetrafluoropropene was 1.7%.

Example 21

The same operation as in example 16, except that the contact time was changed to 50 seconds, the reaction result was: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 100%, the selectivity for E-1,3,3, 3-tetrafluoropropene was 92.4%, the selectivity for Z-1,3,3, 3-tetrafluoropropene was 4.1%, and the selectivity for 1,1,1,3, 3-pentafluoropropane was 3.5%.

Example 22

The same operation as in example 16, except that the contact time was changed to 100 seconds, the reaction result was: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 100%, the selectivity for E-1,3,3, 3-tetrafluoropropene was 81.6%, the selectivity for Z-1,3,3, 3-tetrafluoropropene was 5.9%, and the selectivity for 1,1,1,3, 3-pentafluoropropane was 12.5%.

Example 23

The same operation as in example 16 was conducted, except that the molar ratio of E-1-chloro-3, 3, 3-trifluoropropene to anhydrous hydrogen fluoride was changed to 1: 5, the reaction result is: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 86.3%, the selectivity for E-1,3,3, 3-tetrafluoropropene was 97.1%, and the selectivity for Z-1,3,3, 3-tetrafluoropropene was 2.9%.

Example 24

The same operation as in example 16 was conducted, except that the molar ratio of E-1-chloro-3, 3, 3-trifluoropropene to anhydrous hydrogen fluoride was changed to 1: 20, the reaction result is: the conversion of E-1-chloro-3, 3, 3-trifluoropropene was 100%, the selectivity for E-1,3,3, 3-tetrafluoropropene was 91.3%, the selectivity for Z-1,3,3, 3-tetrafluoropropene was 2.8%, and the selectivity for 1,1,1,3, 3-pentafluoropropane was 5.9%.

Example 25

The same operation as in example 16 was conducted, except that E-1-chloro-3, 3, 3-trifluoropropene was replaced with Z-1-chloro-3, 3, 3-trifluoropropene in an equivalent amount, and the reaction results were: the conversion of Z-1-chloro-3, 3, 3-trifluoropropene was 100%, the selectivity for E-1,3,3, 3-tetrafluoropropene was 93.2%, and the selectivity for Z-1,3,3, 3-tetrafluoropropene was 6.8%.

Example 26

A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of the 1,1,1,3, 3-pentafluoropropane is 6s, and the reaction pressure is 0.1 MPa. After running for 20h, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of 1,1,1,3, 3-pentafluoropropane was 96.3%, the selectivity to E-1,3,3, 3-tetrafluoropropene was 87.2%, and the selectivity to Z-1,3,3, 3-tetrafluoropropene was 12.8%.

From the results of example 26, it can be seen that 1,1,1,3, 3-pentafluoropropane, which is a by-product of the vapor phase fluorination reaction of E-1-chloro-3, 3, 3-trifluoropropene and/or E-1-chloro-3, 3, 3-trifluoropropene, can be recycled to the fluorination reaction for further reaction, and further conversion to E-1,3,3, 3-tetrafluoropropene can be continued.

Example 27

A tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm was charged with 10mL of the catalyst prepared in example 1. The reaction conditions are as follows: the reaction temperature is 400 ℃, the contact time of Z-1,3,3, 3-tetrafluoropropene is 6s, and the reaction pressure is 0.1 MPa. After running for 20h, the reaction product was washed with water, washed with alkali and dried, and the gas phase organic phase was taken for GC analysis. The reaction result is: the conversion of Z-1,3,3, 3-tetrafluoropropene was 72.1% and the selectivity of E-1,3,3, 3-tetrafluoropropene was 99.9%.

From the results of example 27, it can be seen that E-1-chloro-3, 3, 3-trifluoropropene and/or Z-1,3,3, 3-tetrafluoropropene, which is a by-product of the gas phase fluorination reaction of E-1-chloro-3, 3, 3-trifluoropropene, can be recycled to the fluorination reaction for further reaction and conversion to E-1,3,3, 3-tetrafluoropropene can be further carried out.